JP3372848B2 - Electron emitting device, image display device, and manufacturing method thereof - Google Patents

Electron emitting device, image display device, and manufacturing method thereof

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Publication number
JP3372848B2
JP3372848B2 JP29710797A JP29710797A JP3372848B2 JP 3372848 B2 JP3372848 B2 JP 3372848B2 JP 29710797 A JP29710797 A JP 29710797A JP 29710797 A JP29710797 A JP 29710797A JP 3372848 B2 JP3372848 B2 JP 3372848B2
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Japan
Prior art keywords
electron
substrate
emitting device
metal
fine particles
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JP29710797A
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JPH10188778A (en
Inventor
正人 山野辺
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キヤノン株式会社
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Priority to JP29020596 priority
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Priority to JP29710797A priority patent/JP3372848B2/en
Publication of JPH10188778A publication Critical patent/JPH10188778A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02Manufacture of electrodes or electrode systems
    • H01J9/022Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02Main electrodes
    • H01J1/30Cold cathodes, e.g. field-emissive cathode
    • H01J1/316Cold cathodes, e.g. field-emissive cathode having an electric field parallel to the surface, e.g. thin film cathodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00Electron emission display panels, e.g. field emission display panels

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron-emitting device, a display device, and a method for manufacturing them, and particularly to an electron terminated by a low work function material through a carbon body grown by using fine metal particles as a nucleus through oxygen. The present invention relates to an electron-emitting device using fine particles of an emitter, a display device using the electron-emitting device, and a method for manufacturing the electron-emitting device.

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices are known, which are a thermoelectron-emitting device and a cold cathode electron-emitting device. Examples of the cold cathode electron emitting device include a field emission type electron emitting device, a metal / insulating layer / metal type electron emitting device, a surface conduction type electron emitting device, and a semiconductor type electron emitting device.

As a semiconductor-type electron-emitting device, there is an example in which a strong reverse electric field is applied to a p-type / n-type semiconductor by Gorkom et al. And electrons are emitted by utilizing the avalanche phenomenon. Further, as an example of the field emission type electron-emitting device, C.
A.Spindt, "Physical propertyof thin film field emis
sion cathodes with molybdenum cones ", J.Appl.Phys.,
The literature of 47, 5248 (1976) is known.

In the field emission type electron-emitting device, as described in the above-mentioned document, an electron-emitting body having a three-dimensionally sharp tip is arranged on a conductor on a substrate.
It is called a gate electrode, and it is located between the tip of the electron emitter and 10
Spindt with a structure having an electrode with an opening that draws out electrons into a vacuum by generating a strong electric field of about 7 V / cm
Type field emission devices are common. Further, in order to form the image display device, an anode provided with a phosphor is arranged on the upper surface in the direction perpendicular to the substrate. Such an image display device performs display by applying a voltage to the anode and causing electrons to collide with the phosphor to emit light. On the other hand, in this field emission electron-emitting device,
One having a structure in which a metal film is two-dimensionally processed into a triangle or a rectangle, and electrons are emitted from the tip or corner of the metal film in parallel with the substrate by an electric field between counter electrodes installed on the substrate is there. This is generally called a lateral field emission type electron emitting device.

In these field emission electron-emitting devices, conventionally, in order to emit electrons, the tip of the electron emitter is sharply pointed, the electric field is concentrated there, and a strong electric field is applied. Highly melting metal materials W and M
Although the use of o and the like as an electron emitter has been studied, there has been a problem in that the electron emission current changes with time due to deformation of the shape of the tip of the electron emitter, that is, deterioration. In recent years, by using diamond or the like, which is said to have a low work function or a negative electron affinity, as an electron emitter, a proposal to obtain an emission current in a low electric field without sharply sharpening the electron emitter has been announced. is there. For example, C.Xie; SID
International Symposium Digest Technical paper, pp4
3 (May, 1994 and US Pat. No. 5,180,951).

Further, in US Pat. No. 5,463,271, 50% or more of carbon, preferably conductive diamond, has an electrically negative Cs, which is electrically positive due to oxygen or fluorine. It is disclosed that K, Na, Ba and the like are chemically bound to reduce the work function to improve electron emission characteristics.

Attempts have also been made to arrange a plurality of these electron-emitting devices and combine them with a phosphor to form a color flat panel. In these flat panels, a group of a plurality of electron-emitting devices is installed on the substrate for each pixel of the phosphor, and an arbitrary electron-emitting device group is selected according to an image signal to control the electron emission amount. The arrangement of electron-emitting devices, phosphors, and control electrodes have been devised in order to perform gradation display. For example, in the aforementioned semiconductor-type electron-emitting device, there is an example in which electron-emitting devices provided on a semiconductor substrate are arranged in a matrix and combined with a control electrode to select an arbitrary electron-emitting device and control the amount of electrons.

Further, in the aforementioned Spindt type, row-direction wirings are installed on the substrate, electron-emitting devices are connected to the row-direction wirings, and control electrodes (the aforementioned gate electrodes) orthogonal to the row-direction wirings are arranged in the column direction. , And the electron emission elements located at the intersections of the row-direction wiring and the column-direction wiring are selected to control the electron emission amount,
The display device is configured to cause the fluorescent substance to emit light by accelerating and colliding the electrons extracted in the vacuum with the anode having the fluorescent substance arranged to face the substrate.

[0009] In addition, C.Xie literature using diamond or the like having a low work function or a low electron affinity,
In U.S. Pat. No. 544770, a row wiring is provided on a substrate, and a phosphor arranged to face the substrate is provided as a column wiring, and a diamond thin film is partially formed on a row wiring at an intersection of the row wiring and the column wiring. An example of a display device that is installed and selects and controls the electron-emitting device is disclosed.

[0010]

However, in these field emission devices, in consideration of mass productivity, the Spin
In the field emission device of dt type or the like, it has been a problem that three-dimensional processing for sharpening the tip of the electron emitter is performed with good reproducibility. Further, in order to perform modulation at a lower voltage, it is necessary to process the opening (aperture) of the gate electrode in the order of submicrons, and reproducibility is a problem because it is ultrafine processing. . In the case where diamond is used as the electron emitter, the diamond has a low work function or has a negative electron affinity, so that electrons can be emitted in a low electric field, so that the unique display panel configuration described above is possible. It is said that the method of forming the diamond that becomes the electron emitter is Laser ablation.
Since it is a method of forming by the method etc., it has various problems such as the problem of increasing the area, the shape of the diamond as an electron emitter, the controllability of the density, the control of the physical properties of the surface of the diamond, etc. The current situation is that it has not been put to practical use due to the problem of commercialization.

The present invention is particularly applicable to an electron-emitting device which can be driven at a low voltage, has high uniformity, and is excellent in mass productivity, and an image display device using the same, such as a color flat panel having excellent display quality, and a manufacturing method thereof. For the purpose of providing.

[0012]

The preferred embodiments of the present invention will be described below.

The electron-emitting device of the present invention comprises an electrode in which a plurality of fine particles of an electron-emitter in which a low work function material is destroyed is disposed in a carbon body having metal fine particles as a nucleus through oxygen, and the electron. It is an electron-emitting device having an electrode for applying a voltage for drawing electrons from an emitter into a vacuum.

The preferred embodiment of the electron-emitting device will be described in detail below. In the electron-emitting device of the present invention, a carbon body is formed with the fine metal particles formed in advance as nuclei, and oxygen is added to the carbon body to lower the amount. A plurality of fine particles of an electron emitter terminated by a work function material are partially arranged in a desired form on a first electrode on a first substrate, and a voltage for drawing electrons into a vacuum is applied. It is an electron-emitting device including a second electrode for

The second electrode for applying a voltage for drawing the electrons into the vacuum is the first electrode on the first substrate.
Is disposed on the second base so as to face the electrode.

Further, a second electrode for applying a voltage for drawing out the electrons into a vacuum is disposed on a support which is electrically insulated from the first electrode on the first substrate, and the electron is further added. A third electrode for accelerating the is provided.

Preferably, the metal of the metal fine particles is a catalytic metal for forming the carbon body, and is Ni or C.
The iron group such as o and Fe, or the platinum group such as Pd or Ir and Pt, and the carbon body is graphite (so-called HOP).
Including G 1) , PG 2) and GC 3) , HOPG is an almost perfect graphite crystal structure, PG is a crystal grain with a grain structure of about 200 angstroms and the crystal structure is somewhat disordered, and GC is a crystal grain of about 20 angstroms. It means that the disorder of the crystal structure is further increased. HOPG 1)
High Oriented Pyrolytic Graphite, PG 2) Pyroli
tic Graphite pyrolytic carbon, GC 3) indicates Glassy Carbon amorphous carbon. ), Amorphous carbon (amorphous carbon and amorphous carbon and the graphite)
The above-mentioned low work function material is an alkali metal such as K, Rb, Cs, Ca, Sr, or Ba, or an alkaline earth metal.

Further, it is preferable that the metal material of the first electrode material and the metal fine particles are different from each other, and a resistor serving as a current limiting resistance is preferably provided between the first electrode and the metal fine particles.

The particle size of the electron emitting particles depends on the particle size of the metal particles, but the particle size of the metal particles is 3 to 100.
nm, and the metal fine particle density is 10 9 to 10 12 particles / cm
2 , and the distance between the metal fine particles is preferably equal to or larger than the particle diameter of the metal fine particles. The particle size, density, and material of the metal fine particles are set appropriately. Further, the carbon body is preferably a few atomic layers or less.

The low work function material is preferably used in a layer of several atomic layers or less, more preferably 1 atomic layer or less.

According to the electron-emitting device of the present invention, the fine particles of the electron-emitter terminated by the low work function material are introduced into the carbon body formed by using the metal fine-particles as nuclei through oxygen,
Since the fine particles having a desired shape and partially arranged on the electrode on the substrate are stable and have a low work function, the fine particles function as an electron emitter, so that electron emission is possible in a low electric field, and the particles are opposed to it. Even with a configuration in which an electrode for applying a voltage for drawing out electrons into a vacuum is provided, it is possible to drive at a low voltage. Furthermore, the metal of the metal fine particles is a catalytic metal for forming a carbon body, which is an iron group such as Ni, Co or Fe,
Since it is a platinum group of Pd, Ir, and Pt, it is possible to grow graphite, which is a stable carbon body, at low temperature by using metal fine particles as nuclei.

Further, by using a material different from the metal material of the first electrode material and the metal fine particles, the carbon body is selectively formed in the region where the metal fine particles are formed.

Since a bond is formed with the alkali metal such as K, Rb, Cs, Ca, Sr, or Ba which is the low work function material through the carbon body and oxygen, it is stable. A low work function electron emitter can be provided.

Next, in a preferred embodiment of the method for manufacturing an electron-emitting device of the present invention, (1) an organic metal-containing liquid is applied onto an electrode arranged on a substrate, which comprises the following steps. A step of thermally and thermally decomposing (also referred to as firing) in a desired atmosphere to form metal fine particles or fine particles composed of carbon fine particles and metal fine particles on the electrode.

(2) A step of introducing a carbon-containing material into the substrate and decomposing it by heat or the like to form a carbon body on the metal fine particles.

(3) A step of heating the substrate in an atmosphere containing oxygen or generating plasma to terminate oxygen on the surface of the carbon body.

(4) A step of introducing a low work function material into the substrate and coating fine particles of metal and carbon with the low work function material.

(5) A step of heating the substrate.

In the step (1), a spinner coating method or an ink jet method is used as a method for applying the organic metal-containing liquid to the substrate. However, the ink jet method is effective in that fine droplets can be efficiently and accurately controlled. Preferably, a desired pattern can be formed by applying the droplets to the substrate by the inkjet method.

The density, particle size, and distance between particles of the metal fine particles are
It is controlled by controlling the concentration of the metal component of the organic metal-containing liquid, the droplet shape, the temperature of the thermal decomposition step, and the like. Furthermore,
After forming the metal fine particles, it is also possible to stare the metal fine particles by heating in a vacuum or a hydrogen atmosphere to form larger fine particles.

In the above step (2), the material having carbon means C n H 2n + 2 such as methane, ethane and propane.
Saturated hydrocarbon represented by, ethylene, propylene, etc. C
Examples include unsaturated hydrocarbons represented by composition formulas such as n H 2n, and other examples include cyclic hydrocarbons such as benzene. A diluent gas may be used as appropriate. The diluent gas is hydrogen gas, a gas containing fluorine, or the like, or an inert gas such as helium.

Further, heat means a substrate (the above-mentioned first substrate).
It is heat for heating, and a voltage may be applied between the first electrode and the second electrode during this heating.

In the above step (3), the atmosphere containing oxygen means an atmosphere under an appropriate partial pressure of oxygen or a mixed gas of oxygen and an inert gas (helium or the like) or oxygen and N 2 . It may be under reduced pressure or atmospheric pressure. The heating temperature and oxygen partial pressure are selected so that the carbon body formed in step (2) does not burn with oxygen and the carbon body and oxygen are terminated.

Further, in the step (5), the heating temperature is selected such that only the low work function material bonded to oxygen terminated with carbon remains and the unbonded low work function material is removed by evaporation.

At this time, a voltage may be applied between the first electrode and the second electrode to use both electric energy and heat generated by heating.

According to the method of manufacturing the electron-emitting device of the present invention, the organic metal-containing liquid is applied onto the electrode arranged on the substrate, and then the material is heated and pyrolyzed in a desired atmosphere (also referred to as firing). Since metal fine particles or fine particles composed of carbon fine particles and metal fine particles are formed, the organic metal-containing liquid can be thermally decomposed at low temperature to form metal fine particles, and the density of the metal fine particles is equal to that of the organic metal-containing liquid. It is controlled by the concentration of the metal component, and the particle size of the metal fine particles can be formed with good controllability by controlling the metal concentration of the metal-containing liquid, the droplet shape, and the temperature of the thermal decomposition step. Furthermore, since the organic metal-containing liquid is applied to the substrate as droplets by the inkjet method, it can be directly formed only on a desired portion without relying on photolithography or the like, so that it is inexpensive, highly uniform, and highly mass-producible. A manufacturing method can be provided.

A material having carbon is introduced with the metal fine particles as a nucleus and decomposed and grown by heat or the like. Therefore, a carbon body having a core of the metal fine particles, and further, a carbon body having a controllability of the metal fine particles is maintained. An electron emitter having metal fine particles as a nucleus is formed.

The base is heated in an atmosphere containing oxygen or plasma is generated to terminate oxygen on the surface of the carbon body, a low work function material is introduced, and fine particles of carbon body having metal fine particles as nuclei are formed. Because of the coating, the low work function material is bonded to the carbon body through the bond of oxygen. Further, the heating temperature is a temperature at which only the low work function material bonded to oxygen terminating the carbon body remains, and the unbonded low work function material is vaporized and removed. The work function material is coated with a few atomic layers or less.

The structure of the image display device of the present invention comprises the first wiring group of m pieces arranged on the first substrate, and the nth wiring group to which a voltage for drawing out electrons into the vacuum is applied. There are two wiring groups, and the m first wiring groups and the n second wiring groups are substantially orthogonal to each other, and the intersection points (m × n intersection points) thereof are as described above. Of the electron-emitting device of the present invention.

A preferred first configuration of the image display device of the present invention is an n to which a voltage for drawing electrons into a vacuum is applied.
In the image display device, the second wiring of the book and the phosphor are arranged on the second base that faces the first base. In addition, if necessary, a spacer is arranged between the first base and the second base as an atmospheric pressure resistant support member, and the first base and the second base form part of a vacuum container. It may be configured. When the image display device is color, the phosphors provided on the second substrate are red, green, and blue phosphors arranged in stripes.

In a preferred second configuration of the image display device of the present invention, the n second electrodes to which a voltage for drawing out electrons into a vacuum is applied are on the m first electrodes. The image display device includes an electrode which is disposed on an electrically insulated support and further has an electrode having a phosphor to which a voltage for accelerating electrons is applied.

In the first structure of the image display apparatus of the present invention, the first wiring and the second wiring are selectively scanned by the first wiring in accordance with the image signal, and at the same time, the second wiring is also scanned. A modulation signal is input to the wiring of, the electron corresponding to the image signal is emitted from the electron-emitting device at each intersection, and the accelerated electron collides with the phosphor of each pixel of the second wiring group, It emits light and an image is displayed. Further, the distance between the first substrate and the second substrate and the potential for accelerating the electrons are appropriately set according to the electric field intensity of the electron-emitting device that emits electrons and the emission intensity of the phosphor. The distance between the first substrate and the second substrate is 10μ
~ 500μ, the potential for accelerating electrons is 100V ~ 500
0V is preferably used. The modulation signal is preferably pulse width modulation.

According to the first configuration of the image display device of the present invention, the first wiring and the first wiring provided on the first base body are provided.
And a second wiring having a phosphor, which is disposed on the second base opposite to the first base, and the m first wires and the n second wires are substantially orthogonal to each other. And the intersection (m ×
Since the (n number of intersection points) are composed of the electron-emitting devices of the present invention described above, each pixel of the image display device is an intersection point of the first wiring and the second wiring, which is complicated. Positioning accuracy between the first base and the second base is not required.
Further, the shape of the emitted phosphor is almost the same as the area of the electron-emitting device where the electron-emitting device is installed, and the electron beam emitted from the electron-emitting device is provided on the second substrate because the electron orbit does not spread. Since it reaches the phosphor, a high-definition image is displayed. The electron-emitting device of the present invention can emit electrons in a low electric field, is stable, and has high uniformity, so that an inexpensive display device having excellent display performance can be provided.

Further, in the above-mentioned second structure of the image display device of the present invention, the second wiring is provided with the above-mentioned gate electrode to which a voltage for drawing out electrons from the electron-emitting device into a vacuum is applied. Play a role of. The second wiring is
It has an opening (aperture) through which the electron beam emitted from the electron-emitting device passes. Further, an electrode having a phosphor is formed on the second substrate facing the substrate.

With respect to the first wiring and the second wiring, the first wiring is selectively scanned according to an image signal, and at the same time, the modulation signal is input to the second wiring, and the intersections of the intersections are input. Electrons corresponding to the image signal are emitted from the electron-emitting device, and the phosphor corresponding to each pixel on the second substrate that accelerates the electron beam from the opening emits light to display an image.

If necessary, a spacer is arranged between the first base and the second base as an atmospheric pressure resistant supporting member, and the first base and the second base are vacuum containers. May form a part of. When the display device is a color device, the phosphors provided on the second substrate are red, green, and blue phosphors arranged in stripes, and the electrodes having the phosphors are It is common to the phosphors of each color.

According to the second structure of the image display device of the present invention, the m first wirings provided on the base and the n first wirings electrically insulated from the first wirings are provided. A second wiring, and the m first wirings and the n second wirings are substantially orthogonal to each other, and the above-described present invention is provided on the first wiring at the intersection thereof. The electron-emitting device is provided, and a voltage for drawing out electrons from the electron-emitting device into a vacuum is applied to the second wiring to function as a modulation electrode. Also, the second
Since the wiring has an aperture that allows the electron beam emitted from the electron-emitting device to pass through, the electron beam generated from the electron-emitting body can be controlled to have a desired shape. Further, an electrode having a phosphor is formed on the second substrate facing the substrate, and 5000 V to 10000
Since a high voltage of V can be applied at a constant voltage, a high-acceleration phosphor can be applied, and a bright and high-definition image display device can be provided.

The method of manufacturing the first image display device of the present invention preferably includes the following steps.

(1) After the first wiring is formed on the first substrate, the organic metal-containing liquid is applied on the first wiring, and then the material is heated and pyrolyzed (baked) in a desired atmosphere. (Also referred to as), a step of forming metal fine particles or fine particles composed of carbon fine particles and metal fine particles.

(2) A step of introducing a material having carbon into the base and decomposing it by heat or the like to form a carbon body.

(3) A step of forming a second electrode and a phosphor on the second substrate.

(4) A support frame is provided between the first substrate and the second substrate, and if necessary, a spacer is provided between the first substrate and the second substrate as an atmospheric pressure resistant support member. Install and form a vacuum container.

(5) A step of terminating oxygen on the surface of the carbon body by heating or generating plasma in the atmosphere containing oxygen in the vacuum vessel.

(6) A step of introducing a low work function material into the vacuum container to coat fine particles of carbon body having metal fine particles as nuclei.

(7) A step of heating the vacuum container while exhausting it.

(8) A step of sealing the vacuum container.

The steps of the manufacturing method of the present invention are not limited to the order according to the above steps, and the vacuum container may be formed after the electron-emitting device is formed. In this case, the steps (1), (2), (5), (6), (3), (4),
You may perform in order of (7) and (8). However, in this case,
The steps (1), (2), (5), and (6) of forming the electron-emitting device are performed by setting the first substrate in a vacuum chamber or the like.
In addition, the step (3) is changed to the steps (1), (2), (5), (6).
It may be done in advance before.

According to the method of manufacturing an image display device of the present invention, a display device having stable display characteristics and excellent display characteristics can be manufactured. Furthermore, the manufacturing method of the electron emitter and the process of the image display device can be simplified. For example,
By performing the steps (4) and (5) at the same time, an inexpensive display device can be manufactured. Further, the above-described second image display device of the present invention can also be manufactured by the same method as the manufacturing method of the first image display device.

[Operation] According to the electron-emitting device of the present invention,
A plurality of fine particles of an electron-emitter terminated by a low work function material are partially arranged in an electrode on a substrate in a desired form through oxygen on a carbon body formed by using metal fine particles as nuclei, Since an electrode for applying a voltage to pull out electrons into a vacuum is provided, it is not necessary to perform three-dimensional processing for sharpening the tip of the electron emitter or submicron ultra-fine processing for the gate electrode. Since the work function is lowered, an electron-emitting device that can emit electrons in a low electric field can be provided.

Further, according to the method for manufacturing an electron-emitting device of the present invention, after the organic metal-containing liquid is applied on the electrode arranged on the substrate, it is heated and pyrolyzed in a desired atmosphere (both firing is performed). Since the metal fine particles or the fine particles composed of carbon fine particles and metal fine particles are formed, the organic metal-containing liquid can be thermally decomposed at a low temperature to form metal fine particles, and the density of the metal fine particles is It is controlled by the concentration of the metal component of the liquid, and the particle size of the metal fine particles can be formed with good control by controlling the metal concentration of the metal-containing liquid, the droplet shape, the temperature of the thermal decomposition step, etc. An electron-emitting device having excellent controllability of shape or density and good reproducibility is produced.

Further, according to the display device using the method for manufacturing an electron-emitting device of the present invention, the above-mentioned problems in the prior art are solved, and the electron-emitting device can be driven at a low voltage and has high uniformity and excellent mass productivity. Further, it is possible to provide an image display device such as a color flat panel excellent in display quality using the same.

[0062]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the drawings. Figure 1
It is a schematic diagram which shows the structural example of the electron-emitting device of this invention. FIG. 2 is a partially enlarged view of the electron-emitting device of the present invention.

In FIG. 1, FIG. 1A is a plan view of a first substrate formed by the electron-emitting device of the present invention, and FIG. 1B is a sectional view of the electron-emitting device of the present invention. 1 is the first substrate,
2 is a second substrate, 3 is a first electrode, 4 is a second electrode, 5
Is an electron emitter, and 6 is a phosphor installed when used as an image display device.

FIG. 12 shows a case where the phosphor 6 is not installed. In the figure, the same symbols as those in FIG. 1 are the same.

2A and 2B are partially enlarged sectional views of the first substrate 1, the first electrode 3 and the electron emitter 5 of FIG.
It is a top view. In FIG. 2, two of the electron emitters 5 are
Reference numeral 1 is metal fine particles, 22 is a carbon body, and 23 is a low work function material.

The feature of the present invention is that, as shown in FIG. 1, a plurality of fine particles 21 of the electron emitter 5 are partially arranged in a desired form on the electrode 3 on the substrate 1, and electrons are vacuumed. An electrode 4 for applying a voltage for drawing out is arranged therein, and further, as shown in FIG. 2, the electron emitter 5 is an oxygen atom in a carbon body 22 formed as a core of the metal fine particle 21. Is the electron emitter 5 terminated by the low work function material 23 through the.

FIG. 3 is an example of a manufacturing process flowchart of the electron-emitting device of the present invention. Below, along the process chart,
explain.

Step (1) The substrate 1 is thoroughly washed with a detergent, an organic solvent, pure water and the like, and after depositing the material of the electrode 3 by a vacuum deposition method, a sputtering method or the like, a photolithography technique is used. The electrode 3 is formed on the substrate 1. After applying an organic metal-containing liquid onto the electrode 3 by an inkjet method or the like, it is heated and pyrolyzed (also referred to as firing) in a desired atmosphere to form metal fine particles or fine particles composed of carbon fine particles and metal fine particles. To do.

A spinner coating method or an inkjet method is used as a method for applying the organic metal-containing liquid to the substrate 1, but the inkjet method is preferably applied to the substrate 1 as droplets. The inkjet method uses a piezo jet method of ejecting a liquid by the energy of a piezoelectric element, a bubble jet method of ejecting a liquid by applying thermal energy to the liquid, or the like, in a desired pattern,
It is formed. As the organic metal-containing liquid, an aqueous solution of an organic complex of metal is preferably used.

In the preferred method of manufacturing an electron-emitting device of the present invention, a liquid containing an organic metal is applied onto the conductive thin film on the substrate 1 in the form of droplets. In particular, the inkjet method is preferable in that minute droplets can be efficiently and accurately controlled. According to the inkjet method, it is possible to reproducibly generate minute droplets of 10 nanograms to several tens of nanograms and apply them to the substrate. The inkjet method is roughly classified into two types. One is a bubble jet method in which a liquid containing the organometallic liquid is heated and foamed by a heating resistor to eject droplets from a nozzle,
The other is a piezo jet method in which a liquid droplet containing the organometallic liquid is ejected by the contraction pressure of a piezo element arranged in a nozzle.

An example of the ink jet type apparatus used in the present invention is shown in FIGS. In FIG. 4, a bubble jet method is shown, 131 is a substrate, 132 is a heat generating part, 133 is a support plate, 134 is a liquid flow path, 135 is a first nozzle, 136 is a second nozzle, and 137 is an ink flow path partition wall. 138 and 139 are liquid chambers containing an organometallic liquid, 1310 and 1311 are liquid supply ports containing an organometallic liquid, and 1312 are ceiling plates, respectively, facing the first nozzle 135 and the second nozzle 136. The organometallic liquid is jetted onto the first substrate 1 that is arranged.

FIG. 5 shows a piezo jet system, in which 141 is a glass first nozzle, 142 is a glass second nozzle, 143 is a cylindrical piezo element, and 14 is a glass piezo element.
5, 146 are organometallic liquid supply tubes, 147 are input terminals for supplying electric signals to the cylindrical piezo element 143, 1
Reference numerals 48 denote fixed substrates, respectively, and the first glass nozzle 1
The organometallic liquid is jetted from the tips of 41 and 142 to the opposing first substrate 1. Although two nozzles are shown in FIGS. 4 and 5, the present invention is not limited to this.

The density of the fine metal particles, which is a feature of the present invention, is
Controlled by the concentration of the metal component of the organometallic-containing liquid,
The particle size of the metal fine particles can be controlled by controlling the metal concentration of the metal-containing liquid, the droplet shape, the temperature of the thermal decomposition step, the atmosphere, etc.
Controlled.

The atmosphere of the thermal decomposition step means an oxygen-containing atmosphere such as the atmosphere or a hydrogen-containing atmosphere. In the oxygen-containing atmosphere, when the easily oxidizable metal material is decomposed as an organic metal material, a metal oxide may be formed,
In this case, it is reduced to a metal by heating in a vacuum or hydrogen atmosphere.

Step (2) The substrate 1 is placed in the vacuum processing apparatus shown in FIG. 6, the same parts as those shown in FIG. 1 are designated by the same reference numerals. That is, 1 is a first substrate, 3 is a first electrode, and 5 is an electron emitter.
Further, 61 is a vacuum container, 62 is an exhaust pump, 6
Reference numerals 3 and 64 are electrodes for plasma generation. Reference numerals 65 and 69 are carbon-containing material sources, 66 is an oxygen cylinder, 67 is a low work function material generation source, 68 is a power source for plasma generation, and an electron emission element is provided in the vacuum container 61. Material is arranged.

The vacuum container 61 is provided with equipment necessary for measurement in a vacuum atmosphere, such as a vacuum gauge (not shown).
The measurement and evaluation can be performed in a desired vacuum atmosphere. In addition, after connecting the measurement vacuum chamber 105 of FIG. 10 by a load lock method and forming the electron-emitting device by the vacuum processing apparatus 61 of FIG. 6, the electron-emitting device is installed in the measurement vacuum chamber 105 of FIG. You may move and measure.

The exhaust pump 62 is composed of a normal high vacuum system including a turbo pump and a rotary pump, and an ultra high vacuum system including an ion pump. Reference numerals 65 and 69 are material sources having carbon, 69 gas cylinders in the case of gas, and ampoules having 65 liquid in the case of liquid, which are introduced into the vacuum container 61. The entire vacuum processing apparatus provided with the electron-emitting devices shown here can be heated up to 300 degrees by a heater (not shown). Further, the substrate 1 can be heated up to 800 ° C. After sufficiently evacuating the vacuum processing apparatus, a material having carbon is introduced into the apparatus. The whole vacuum processing apparatus and the substrate 1 were heated by a heater, and the organic material gas introduced from the carbon-containing material sources 65 and 69 contacted the catalytic metal fine particles to be thermally decomposed, thereby being prepared in the step (1). A carbon body is selectively grown and covered with the metal fine particles as a nucleus. still,
The heating of the vacuum processing apparatus is performed by the carbon source 65, 69.
It is carried out at a temperature at which the introduced organic material gas is suppressed from adsorbing to the wall of the vacuum processing apparatus. Therefore, the heating temperature of the vacuum processing apparatus is preferably lower than the heating temperature of the substrate 1. Then, it is evacuated to a vacuum. The heating temperature is appropriately selected and set depending on the particulate metal material, introduced gas, and the like.

Step (3) An appropriate amount of oxygen is introduced into the vacuum container 61 from the oxygen cylinder 66, the substrate 1 is heated in an atmosphere containing oxygen, and the plasma generating electrode 63, Plasma is generated between 64 or between the plasma generating electrode 63 and the first electrode 3 of the substrate 1 to terminate oxygen on the surface of the carbon body. Then, it is evacuated to a vacuum.

This process can also be achieved by setting an atmosphere containing oxygen under heating without generating plasma.

Step (4) Source 67 of low work function material
As a result, a low work function material is introduced into the substrate 1, and carbon particles having metal particles as cores are coated with the low work-related material. At this time, the low work function material is laminated in several atomic layers or more.

Step (5) The substrate 1 is heated to evaporate the low work function material that is not bonded to oxygen on the surface of the carbon body among the low work function materials that coat the fine particles of the carbon body. Then, the coating layer of the low work function material is a monoatomic layer or a layer of several atomic layers or less.

FIG. 11 is a schematic diagram showing a second configuration example of the electron-emitting device of the present invention. In FIG.
FIG. 11A is a plan view on the first substrate 1 by the electron-emitting device of the present invention, and FIG. 11B is a sectional view of the electron-emitting device of the present invention. In the figure, 1 is a first substrate, 2 is a second substrate, 3 is a first electrode, 4 is a second electrode, 5 is an electron emitter, and 6 is a phosphor installed when used as a display element. , 7 is a third electrode, and 8 is a support for electrically insulating the first electrode and the second electrode. Note that, in FIG. 11, the same reference numerals as those in FIG.

The characteristics of the second structure of the electron-emitting device of the present invention are the same as those of the first structure of the electron-emitting device of the present invention shown in FIG.

The manufacturing process of the second structure of the electron-emitting device of the present invention is the same as the manufacturing process of the first structure of the electron-emitting device of the present invention shown in FIG. 3, except for the step (1) of FIG. It is a process. Only step (1) will be described, and the remaining steps will be omitted.

Step (1) The substrate 1 is thoroughly washed with a detergent, an organic solvent, pure water and the like, and after depositing the material of the electrode 3 by a vacuum deposition method, a sputtering method or the like, a photolithography technique is used. The electrode 3 is formed on the substrate 1. An insulating layer 8 made of SiO 2 and an electrode 7 are similarly formed on the electrode 3. Next, after applying an organic metal-containing liquid by an inkjet method or the like, it is heated and pyrolyzed (also referred to as firing) in a desired atmosphere to form metal fine particles or fine particles composed of carbon fine particles and metal fine particles. In the above manufacturing process, the insulating layer 8 such as SiO 2 and the electrode 4 may be formed after the electron emitter is formed.

The configuration of the above-described first image display device of the present invention will be described with reference to FIG. 7A is a sectional view of the image display device of the present invention, FIG. 7B is a lower rear plate diagram, and FIG. 7C is an upper face plate diagram. In FIG. 7, 71 is a rear plate, 72 is a support frame that supports the face plate corresponding to the second substrate and the rear plate 71, 73 is a phosphor consisting of red, green, and blue stripes, and 74 is ITO or the like. A transparent electrode which is a second wiring made of, 75 is a face plate on the side for displaying an image,
Reference numeral 76 is a first base, 77 is a first wiring, and 78 is an electron emitter. Although the rear plate 71 and the first base 76 are separate members, the first base 76 may also serve as the rear plate 71.

The image display device has a first wiring 77 arranged on a first base 76 and a phosphor 73 arranged on a second base 75 facing the first base 76. The second wiring 74 is provided, and the m first wirings 77 and the n second wirings 74 are substantially orthogonal to each other. Electron emitters 78 are formed at m × n locations to form the image display device of the present invention.

The first wiring 77 and the second wiring 74 are
The first wiring 77 is selectively scanned according to the image signal, at the same time, the modulation signal is input to the second wiring 74, and an image is obtained from an electron-emitting device having a plurality of electron-emitting bodies 78 at each intersection. Electrons corresponding to the signal are emitted and accelerated, and the accelerated electrons collide with the phosphor 73 of each pixel of the second wiring 74 to emit light, and an image is displayed.

The image display device of the present invention may have the following configuration. FIG. 8 shows the configuration of the second image display device of the present invention.
A description will be given using (a) and (b). FIG. 8A is a cross-sectional view of the second image display device of the present invention, and FIG. 8B is a lower rear plate view. In FIG. 8, reference numeral 72 is a support frame for supporting the face plate and the rear plate, 85 is a phosphor, 80 is a transparent electrode such as ITO, 75 is a face plate, 76 is a first substrate also serving as a rear plate, and 77 is a first base. 1 wiring, 78 is an electron emitter, 81 is an aperture 82
A second wiring having a reference numeral 82, an opening (aperture) through which an electron beam generated from the electron emitter 78 passes, a reference numeral 83
Is the first wiring 77 and the second wiring 77 provided on the first substrate 76.
This is a support body that electrically insulates the wiring 81 from the wiring 81 and is an insulating layer such as SiO 2 .

The first wiring 77 arranged on the first base 76 and the second wiring 81 having the aperture 82 arranged on the first base 76 via the insulating layer 83 are respectively formed. The m first wirings 77 and the n second wirings 81
Are substantially orthogonal to each other, and the first wiring 77 at the intersection
, A plurality of electron emitters 78 are formed in m × n places,
An electron-emitting device is formed at each intersection, and a transparent electrode 86, a phosphor 84, and a metal back 85 are further arranged to form an image display device of the present invention.

Further, the phosphors 84 are composed of red, green and blue phosphors, respectively, which are applied in stripes, and the transparent electrode 86 is made of red,
It has a function of a common electrode for each of the green and blue phosphors.
Black stripes are provided between the red, green and blue phosphors.

The first wiring 77 and the second wiring 81 are
The first wiring 77 is selectively scanned according to the image signal, and at the same time, the modulation signal is input to the second wiring 81, and an image is obtained from an electron-emitting device including a plurality of electron-emitters 78 at each intersection. Electrons corresponding to the signal are emitted, and the transparent electrode 86,
The electron beam accelerated by the voltage applied to the metal back 85 collides with the phosphor 84 of each pixel corresponding to the opening portion (aperture) 82 of the second wiring 81 and emits light, which is directed to the observer above. Image is displayed.

An example of the method of manufacturing the configuration of the first image display device shown in FIG. 7 according to the present invention is provided by the process flow chart shown in FIG. Hereinafter, description will be given with reference to process drawings.

Step (1) After the first wiring 77 is formed on the first substrate 76, the organic metal-containing liquid is applied on the first wiring 77, and then heated under a desired atmosphere. Decomposes (also referred to as firing) to form metal fine particles or fine particles composed of carbon fine particles and metal fine particles.

Step (2) The second wiring 74 and the phosphor 73 are formed on the second substrate 75.

Step (3) A support frame 72 for supporting the rear plate 71 on which the first base body 76 is laid and the face plate as the second base body 75 is provided with the first frame, if necessary.
A spacer is also disposed as an atmospheric pressure resistant support member between the base body 76 and the second base body 75, and the rear plate 71 and the face plate 75 form a vacuum container.

Step (4) A material having carbon is introduced into the first substrate 76 and decomposed by heat or the like to form fine carbon particles having metal fine particles as nuclei.

Step (5) An atmosphere containing oxygen is set in the vacuum vessel, and heating or plasma is generated to terminate oxygen on the surface of the carbon body.

Step (6) A low work function material is introduced into the vacuum container, and the carbon particles having the metal particles as cores are coated with the low work function material.

Step (7) While evacuating the vacuum container,
To heat.

Step (8) The vacuum container is sealed.

Although the steps of the manufacturing method of the present invention are performed in several steps, the present invention is not limited to this, and the vacuum container may be formed after the electron-emitting device is formed. In this case, steps (1), (4),
You may perform in order of (5), (6), (2), (3), (7) , and (8).

The electron-emitting device of the present invention comprises an electron source,
Not only image display devices used for televisions and computers, but also micro vacuum tubes, printers and the like can be constructed using the electron-emitting devices, and the application range is not limited to these.

[0104]

【Example】

Example 1 The structure of the electron-emitting device of the present invention is shown in FIG.
It is shown in a plan view and a sectional view of (a) and (b). Reference numeral 1 is a first substrate, 2 is a second substrate, 3 is a first wiring, 4 is a second electrode, 5 is an electron emitter, and 6 is a phosphor. Incidentally, four elements having the same shape are formed on the first base 1.

The method for manufacturing the present electron-emitting device will be described below in order with reference to FIG.

Step (1) First of purified quartz glass
A first electrode 3 having a thickness of 1 is formed on a substrate 1 of
000 Å of Mo was deposited to form four first electrodes parallel to each other. Further, a droplet of a nickel formate aqueous solution is applied to the shape of the electron emitter 5 on the first electrode 3 by an ink jet method called a bubble jet method shown in FIG. 4, and then thermally decomposed at 350 ° C. in the atmosphere. did. Six pieces of the first substrate 1 were prepared by the same operation. The shape obtained by heating and decomposing the droplets applied by the inkjet method is 110
It was approximately circular with a size of μm.

Step (2) The first substrate 1 is set in the vacuum processing apparatus of FIG. 6 and sufficiently evacuated, and then the first substrate 15 is removed.
Evacuation was performed while heating to 0 ° C. to remove water and the like. Furthermore,
By heating in hydrogen at 350 ° C., the nickel oxide fine particles were reduced to nickel metal fine particles. Next, methane was introduced into the vacuum chamber and kept at 10 torr. Next, the temperature of the first substrate 1 was maintained at a temperature of 400 ° C. for 1 hour. By the same operation, the other first substrate 1 created in step 1
Was maintained at temperatures of 500 ° C., 600 ° C. and 700 ° C. for 1 hour. Further, two pieces prepared at 600 ° C. were prepared.

Step (3) Next, the five first substrates 1 were subjected to plasma treatment for 5 minutes in the atmosphere containing oxygen of 100 mtorr.

Process (4) Cs of the low work function material is 4 for each.
It was formed on one sheet of the first substrate 1. One of the first substrates 1 treated at 600 ° C. in step 2 did not form Cs.

Step (5) Next, six first substrates 1
Was heated at 250 ° C. for 1 hour. In addition, as a method of generating Cs, CsN (chicka cesium) was previously installed in the source 67 of the low work function material and heated.

With the six first substrates 1 thus prepared,
The first substrate 1 only in the step (1) and the reducing step in the step (2), 400, 500, 600, 700 in the step (2)
The temperature of the first substrate 1 treated at 600 ° C. in the step (2) and the first substrate 1 except the step (4) is treated at 600 ° C., and the step (3) ) Was not performed on the first substrate 1 by 1-A, B, C, D, E,
Let us call them F and G.

Next, on the second substrate 2, the above step (1) is performed.
Similarly to the above, the transparent electrode 4 was vapor-deposited and then patterned to form five parallel electrodes. Further, after applying the phosphor 6 by the known slurry method, the same patterning as that of the above-mentioned transparent electrode was performed.

The first and second bases 1, 1 thus created
2 was placed in a measuring device including a vacuum chamber and a pump. FIG. 10 shows an electron emission device measuring apparatus of the present invention. 10, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG. That is, 1 is a first substrate, 2 is a second substrate, 3 is a first wiring, 4 is a second wiring by a transparent electrode, 5 is an electron emitter,
6 is a fluorescent substance. Reference numeral 104 denotes a voltage source to which an arbitrary voltage from 0 V to 10000 V can be applied in order to measure the characteristics of the electron-emitting device. 102 is an ammeter for measuring the emission current Ie emitted from the electron-emitting device on the first substrate 1, 103 is a scanning circuit, and 101 is a voltage source for selecting the electron-emitting device. Reference numeral 105 is a vacuum container, and 106 is an exhaust pump. An electron emitting element is arranged in the vacuum container 105.

Further, the vacuum container 105 is provided with equipment necessary for measurement in a vacuum atmosphere such as a vacuum gauge (not shown) so that measurement and evaluation can be performed in a desired vacuum atmosphere. There is. The exhaust pump 106 is composed of a normal high vacuum system including a turbo pump and a rotary pump, and an ultra high vacuum system including an ion pump. The entire vacuum processing apparatus provided with the electron-emitting devices shown here can be heated to 300 ° C. by a heater (not shown). Moreover, the 1st base | substrate 1 can be heated to 800 degreeC.

Each first electrode 3 on the first substrate 1
And the scanning circuit 103 are connected.

The scanning circuit 103 is provided with four switching elements inside, and is schematically shown by S1 to S4 in the drawing. Each switching element is a voltage source 101
Output voltage or 0 [V] (ground level) is selected, and the first electrode 3 on the first substrate 1 is
A voltage source 104 applies a voltage for extracting and accelerating electrons between the selected electron-emitting device and the transparent electrode 4.

Each of the bases 1-A, B, C of the first base 1
D, E, F, and G are arranged in a vacuum container with the distance between the first substrate 1 and the second substrate 2 set to 250 μ, then evacuated, and 4 when the voltage applied to the electron-emitting device is 500V. The emission current Ie was measured as an average value of the emission currents, and the voltage-dependent characteristic of the emission current Ie was observed.

Table 1 shows the measurement results.

[0119]

[Table 1] As shown in Table 1, the emission currents are 1-A, 1-B, 1
In -G, the current was below the detection limit or a very small current.
On the other hand, in 1-C, 1-D and 1-E, stable and large emission current was observed. Further, the emission current shows a sharp increase with respect to the voltage applied to the second electrode 4 on the second substrate 2, and the Fowler-Nordheim plot (Ie / V 2 is plotted against 1 / V is plotted. Here, the emission current is I
e, applied voltage V), it was found to be almost linear. This linear FN characteristic shows that the electron-emitting device is a field emission device. The emission current value in Table 1 is the emission current value when the voltage applied to the second electrode 4 is 500 V, and the distance between the first substrate 1 and the second substrate 2 is set to 250 μ. , The applied electric field is 2 × 10
It was 4 V / cm, which means that the emission current was detected in the low electric field. Further, in Table 1, the emission current is the average current value of the four elements, but there was little variation.

Next, 1-A, B, C of the first substrate 1
Taking out D, E, G, electron microscope, photoelectron spectroscopy (E
SCA) and the like.

In 1-A, Ni fine particles having an average particle diameter of 5 nm were dispersed on the Mo wiring, but carbon and Cs were hardly detected. 1-B, 1-
In G, carbon on Ni fine particles, and
Cs was slightly detected. In 1-C, D, E and F, Ni fine particles are covered with carbon, and further,
In 1-C, D, and E, Cs seemed to cover. Also, in 1-E, C is partially on the Mo wiring.
s was observed. 1-F is TEM (transmission electron microscope)
As a result, it was found that graphite was formed with Ni metal fine particles as nuclei. No carbon was formed on the Mo electrode. The density of Ni fine particles was 2 × 10 11 particles / cm 2 . For the measurement, the number per unit area was observed based on the electron microscope image.

From the above, the following can be estimated.

(1) Due to the structure of Ni / C / Cs, the carbon formation temperature was changed from 400 to 700 ° C., resulting in 500
It has been found that it becomes stable at a temperature of 600 ° C or higher.

(2) Only Ni fine particles do not emit electrons in a low electric field (from the measurement observation result of 1-A).

(3) Even if carbon is present on Ni, if Cs is not present, there is no electron emission in a low electric field (from the measurement and observation result of 1-F).

(4) Even if carbon is present on Ni, no electron is emitted in a low electric field without oxygen plasma treatment (1-G).
(From the measurement and observation results).

(5) The formation temperature of stable carbon with respect to oxygen plasma is 500 to 600 ° C. or higher (1-B,
(From the measurement observation results of C, D, and E).

(6) The Ni fine particles forming a stable carbon body form a stable low work function material surface with Cs, and as a result, emit electrons even in a low electric field (1-C, D, E). From the measurement and observation results of.

(7) By forming Ni metal fine particles, the electron emission amount can be formed with good reproducibility (1-C, D,
(From the measurement and observation result of E).

(8) A carbon body is selectively formed on the Ni metal fine particles on the Mo electrode.

[Example 2] In this example, the metal of the metal fine particles was Pd (palladium), the heating temperature in step 5 of Example 1 was changed from 100 ° C to 300 ° C, and the same measurement as in Example 1 was performed. Observed.

The manufacturing method will be described below in order with reference to FIG.

Step (1) First of purified quartz glass
A first wiring group 3 was deposited on the substrate 1 of No. 1 by sputtering to have a thickness of 1000 angstroms of Mo to form four first electrodes 3 parallel to each other. Further, droplets of an aqueous monoethanolamine palladium acetate solution were applied onto the first wiring group 3 in the shape of the electron emitter 5 by an inkjet method, and then thermally decomposed at 350 ° C. in the atmosphere. Five sheets of the first substrate 1 were prepared by the same operation. The shape obtained by heating and decomposing the droplets applied by the inkjet method was a substantially circular shape of 115 μm.

Step (2) After the first substrate 1 is placed in a vacuum chamber and sufficiently evacuated, the first substrate 1 is set to 150
While heating to ℃, it was evacuated to remove water and the like. Further, it was heated at 200 ° C. in vacuum and reduced to obtain metal palladium fine particles. Next, introduce ethylene into the vacuum chamber and
Hold at rr. Next, the temperature of the first substrate 1 is set to 60
Hold at a temperature of 0 ° C. for 20 minutes. By the same operation, Step 1
5 sheets of the other 1st base | substrate 1 created by were processed.

Step (3) Next, five first substrates 1 were subjected to plasma treatment for 5 minutes in the atmosphere containing oxygen of 100 mtorr.

Step (4) Cs of a low work function material was vapor-deposited on each of the four first substrates 1 by a vacuum vapor deposition method.

Step (5) Next, five first substrates 1
At 100, 150, 200, 250, 300 ℃ 1
Heated for 5 minutes. The electron-emitting devices produced in this process will be referred to as 2-A, B, C, D and E.

Table 2 shows the measurement results. Where the first
A voltage of 500 V was applied to the device between the electrode 3 and the second electrode 4, and the emission current Ie of the device and the voltage dependence and time dependence of this emission current Ie were observed for 30 minutes.

[0139]

[Table 2] As shown in Table 2, the emission current depends on the electron-emitting device 2-
In A and 2-B, the current was large with respect to time change and variation among the respective elements. On the other hand, in 2-C, D, and E, a large emission current was observed stably and with good reproducibility. Also,
The emission current showed a sharp increase with respect to the voltage applied to the second electrode on the second substrate, and was almost linear when Fowler-Nordheim plot was performed.

Next, the 2-A, B, C, and
D and E were taken out and observed with an electron microscope, a micro esca, or the like.

In 2-A and B of the first base 1, fine particles of Pd covered with carbon were dispersed on the Mo wiring, and further covered with Cs. 2-
In C, D, and E, fine particles of Pd were covered with carbon and further covered with Cs, but it was smaller than those in 2-A and B. The fine particle density is 6 × 1
It was 0 11 pieces / cm 2 . For the measurement, the number per unit area was observed based on the electron microscope image.

From the above, the following can be estimated.

(1) Due to the structure of Pd / C / Cs, Cs
As a result of observing the heat treatment temperature of 100 to 300 ° C.,
It was found to be stable above 200 ° C.

(2) Pd fine particles on which stable carbon is formed, the element heated at 200 ° C. or higher forms a stable low work function material surface with Cs, and as a result, there is little variation.
There is little variation with time, and electrons are emitted from a low electric field (from measurement observation results of 2-C, D, and E).

(3) Pd fine particles on which stable carbon is formed cannot form a stable low work function material surface with Cs because an element heated to 150 ° C. or less has excessive Cs.
As a result, the variation is large and the variation with time is also large (from the measurement and observation results of 2-A and B).

[Embodiment 3] In this embodiment, Pt (platinum) is used as the metal of the fine metal particles, the low work function material in the step (4) of the first embodiment is changed, and the other steps are the same as those of the first embodiment. Then, measurement observation was performed. Steps (1), (2), (3),
The description of (5) is omitted because it is similar to that of the first embodiment. still,
Five first substrates 1 were prepared. Moreover, as Pt in the step (1), a monoethanolamine platinum acetate aqueous solution was used. The production temperature in the step (2) was 600 ° C. Also,
In the vacuum vapor deposition method in the step (4), low work function materials Ca, Ba, Sr, and Cs were vapor-deposited on each of the four first substrates 1.

Table 3 shows the measurement results. Where the first
A voltage of 500 V was applied between the electrode 3 and the second electrode 4, and the emission current Ie of the device and the voltage dependence of the emission current Ie were observed.

[0148]

[Table 3] From the above, the following can be estimated.

(1) It was found that the structure of Pt / C / low work function material was uniformly stable.

(2) Pt fine particles on which stable carbon is formed have little variation in any low work function material, and the voltage dependence of the emission current sharply increases with respect to the applied voltage. Also, in this case, electrons can be emitted, and the display light amount can be controlled.

[Embodiment 4] This embodiment is an example in which a method for forming an electron emitter in which the particle size and density of metal fine particles are controlled was examined. The particle size and density of the fine metal particles are required for the type of the organometallic compound material, for example, the form of the organic compound bound to the metal, the content of the organometallic compound, the firing temperature, and the firing rate (up to a certain firing temperature. Speed divided by time)
Controlled by etc. The present example is an example in which the content of the organometallic compound, the firing temperature, and the rate were controlled.

In this example, the metal of the metal fine particles was Pt, the conditions for forming the metal fine particles in the step 1 of the example 1 were changed, and only the step of the step 1 was performed, and the same measurement and observation as in the example 1 were performed. .

Step (1) First of purified quartz glass
A first electrode 3 having a thickness of 1 is formed on a substrate 1 of
000 angstrom of Mo was deposited to form four first electrodes 3 parallel to each other. Furthermore, after applying a droplet of a monoethanolamine platinum acetate aqueous solution onto the first wiring group 3 in the shape of the electron emitter 5 by an inkjet method,
It was decomposed by heating in the atmosphere. By the same operation, the first substrate 1
5 sheets were prepared.

The electron-emitting devices produced in step (1) will be referred to as 4-A, B, C and D. In addition, droplets of a monoethanolamine platinum acetate aqueous solution were applied onto the first electrode 3 in the shape of the electron emitter 5 by an inkjet method, and then thermally decomposed in the atmosphere. Then in hydrogen,
The particles were heated at 350 ° C. to agglomerate the platinum particles to increase the particle size and control the particle density. This sample is 4-E
I will call it. In addition, the shape obtained by thermally decomposing the droplets applied by the inkjet method was almost circular with 110 μm.

In Table 4, the content of the organometallic compound (% by weight of the metal content), the firing temperature (° C), the firing rate (° C / min), the particle size of the metal fine particles (nm) and the density (pieces / piece) cm
2 ) The preparation conditions and observation results of 2 ) are shown.

[0156]

[Table 4] From Table 4, the following can be qualitatively said.

(1) The density of metal fine particles increases as the content of the organometallic compound increases.

(2) The slower the firing rate, the larger the particle size of the metal fine particles.

(3) The particle size of the metal fine particles increases as the firing temperature increases.

(4) Larger particles are formed by calcining the organometallic compound to form metal particles and then aggregating. (5) The particle size of the metal particles is 5 to 50 nm, and the density of the metal particles is It was controlled in the range of 10 9 to 10 11 .

In this way, by controlling the particle size and density of the metal fine particles, the particle size and density of the electron emitter could be easily controlled as in the above-mentioned embodiment.

In addition, the samples 4-A, B, C, D,
E was placed in a vacuum chamber, and an electron-emitting device having the same structure as in Example 1 was prepared. The step (1) is the same as in Example 1, and the steps following the step (1) are shown below.

Step (2) The first substrate 1 is set in the vacuum processing apparatus of FIG. 6 and sufficiently evacuated, and then the first substrate 15 is removed.
Evacuation was performed while heating to 0 ° C. to remove water and the like. next,
Methane was introduced into the vacuum chamber and kept at 10 torr. Next, the temperature of the first substrate is set to 1 at a temperature of 650 ° C.
Held for hours.

Step (3) Next, the five first substrates 1 were placed in an atmosphere containing 100 mtorr of oxygen. On this occasion,
A voltage was applied between the first electrode of the first substrate and the second electrode of the second substrate.

Step (4) Cs of a low work function material was vapor-deposited on the first substrate 1 by the vacuum vapor deposition method.

Step (5) Next, the five first substrates 1
Was heated at 200 ° C. for 10 minutes. At this time, a voltage was applied between the first electrode of the first substrate and the second electrode of the second substrate. The electron emission characteristics of the electron-emitting device thus produced were measured in the same manner as in Example 1. Both devices emitted electrons. The electron emission currents were in the order of the fine particle density shown in Table 4, and the higher the fine particle density, the larger the emission current.

[Embodiment 5] This embodiment is an example in which the elements of Embodiment 1 are used to form an image forming apparatus having the first structure of the present invention. Hereinafter, the manufacturing method will be sequentially described with reference to FIG. 7.

Step (1) A first wiring 77 having a thickness of 1000 is formed by a sputtering method on a first substrate 76 in which a 0.5 μm thick silicon oxide film is formed by a sputtering method on a cleaned soda-lime glass. Depositing Angstrom Mo,
500 first wirings 77 parallel to each other were formed. Further, a droplet of a nickel formate aqueous solution was applied onto the first wiring 77 in the shape of the electron emitter 78 by an inkjet method, and then, it was thermally decomposed in the atmosphere. The shape obtained by heating and decomposing the droplets applied by the inkjet method was a substantially circular shape having a diameter of 110 μm.

Step (2) The first substrate 76 is placed in a vacuum processing apparatus and sufficiently evacuated, and then the first substrate 76 is set to 1
Evacuation was performed while heating to 50 ° C. to remove water and the like. Further, it was heated at 350 ° C. in hydrogen to reduce the nickel oxide fine particles to obtain nickel metal fine particles. Next, methane was introduced into the vacuum chamber and kept at 10 torr. next,
The temperature of the substrate was kept at 550 ° C. for 25 minutes.

Step (3) Next, the first substrate 76 was subjected to plasma treatment for 5 minutes in an atmosphere containing 100 mtorr of oxygen.

Step (4) After the vacuum container was sufficiently evacuated, Ba of a low work function material was vapor-deposited on the first substrate 76 by the vacuum vapor deposition method.

Step (5) Next, the first substrate 76 is set to 2
Heat at 50 ° C. for 1 hour.

Next, in the same manner as in the step (1), a transparent electrode 74 was vapor-deposited and then patterned on the second substrate 74 in advance to form 200 × 3 parallel second wirings 74. Furthermore, after applying the red, green, and blue phosphors 73 by a known slurry method, the same patterning as that of the above-mentioned transparent electrode wiring 74 was performed to form the second substrate 74. These first and second substrates 76 and 74 were bonded with frit glass using a spacer so that the distance of 250 μm could be maintained, and the exhaust pipe was bonded to the first substrate 76 side to form a vacuum container.

After sufficiently exhausting from the exhaust pipe, 30
Further evacuation was performed while heating at 0 ° C. for 2 hours. Finally, the exhaust pipe was chipped off and sealed to complete the vacuum container.

Next, the first and second wirings 7 of the first and second bases 76 and 74 of the display panel shown in FIG. 7B.
The terminals of Nos. 7,74 were connected to a driving driver or the like, and a TV signal was inputted and displayed. As a result, a color image could be displayed on the color flat panel.

[0176]

According to the electron-emitting device of the present invention, fine particles of an electron-emitter terminated by a low work function material are introduced onto a substrate through a carbon body formed with metal fine particles as nuclei through oxygen. Since a plurality of electrodes are partially arranged in a desired form and electrodes for applying a voltage for drawing electrons into a vacuum are arranged, a three-dimensional structure in which the tip of an electron emitter is sharply pointed An electron-emitting device that can emit electrons in a low electric field can be provided because processing and ultra-fine processing of the sub-micron of the gate electrode are unnecessary.

Furthermore, according to the method of manufacturing an electron-emitting device of the present invention, after applying the organic metal-containing liquid on the electrode arranged on the substrate, it is heated and pyrolyzed in a desired atmosphere. Since the metal fine particles or the fine particles composed of carbon fine particles and metal fine particles are formed, the organic metal-containing liquid can be thermally decomposed at a low temperature to form metal fine particles, and the density of the metal fine particles is It is controlled by the concentration of the metal component of the liquid, and the particle size of the metal fine particles can be formed with good control by controlling the metal concentration of the metal-containing liquid, the droplet shape, the temperature of the thermal decomposition step, etc. An electron-emitting device having an excellent shape or density controllability, a large area, and good reproducibility is produced.

Furthermore, according to the display device using the electron-emitting device and the manufacturing method of the present invention, the above-mentioned problems can be solved, the electron-emitting device which can be driven at a low voltage and is excellent in mass productivity, and the electron-emitting device are used. We were able to provide display devices such as color flat panels with excellent display quality.

[Brief description of drawings]

FIG. 1 is a schematic view showing a configuration example of an electron-emitting device of the present invention.

FIG. 2 is a partially enlarged view of the electron-emitting device of the present invention.

FIG. 3 is an example of a manufacturing process flowchart of the electron-emitting device of the present invention.

FIG. 4 is a structural diagram showing an example of an inkjet type header section.

FIG. 5 is a structural diagram showing an example of an inkjet type header portion.

FIG. 6 is a configuration diagram of a vacuum processing apparatus used for manufacturing the electron-emitting device of the present invention.

FIG. 7 is a cross-sectional view and a plan view of a display device according to the present invention.

FIG. 8 is a cross-sectional view and a plan view of a display device according to the present invention.

FIG. 9 is a flowchart of one manufacturing process from the manufacturing of the electron-emitting device to the sealing of the display device of the present invention.

FIG. 10 is a block diagram of an electron-emitting device measuring apparatus according to the present invention.

FIG. 11 is a schematic diagram showing a second configuration example of the electron-emitting device of the present invention.

FIG. 12 is a schematic diagram showing a first configuration example of an electron-emitting device of the present invention.

[Explanation of symbols]

1 1st base | substrate 2 2nd base | substrate 3 1st electrode 4 2nd electrode 5 Electron emitter 6 Phosphor 61 Vacuum container 62 Exhaust pumps 63, 64 Electrode 65 for plasma generation Material source 66 having carbon 66 Cylinder 67 Source 71 of low work function material Rear plate 72 Support frame for supporting face plate and rear plate corresponding to second substrate 73 Phosphor 74 Transparent electrode 75 including second wiring 75 Face plate 76 First substrate 77 The first wiring 78 The electron emitter 81 The second wiring group 82 having the aperture 82 The aperture 83 through which the electron flow generated from the electron emitter 78 passes The second substrate 84 The phosphor 85 The metal back 101 The characteristics of the electron-emitting device are measured. Voltage source 102 for operating an ammeter 103 for measuring an emission current Ie emitted from an element of the substrate 1 a modulation scanning circuit 105 a vacuum Device 106 Exhaust pump 131 Substrate 132 Heat generator 133 Support plate 134 Flow path 135 First nozzle 136 Second nozzle 137 Ink flow path spacing walls 138, 139 Liquid chamber 141 containing organometallic liquid Glass first nozzle 142 Glass Second nozzle 143 Cylindrical piezo elements 145, 146 Liquid supply tube 147 containing organometallic liquid Electrical signal input terminals 1310, 1311 Supply port 1312 for liquid containing organometallic liquid Ceiling plate

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) H01J 1/30-1/316 H01J 9/02 H01J 31/12

Claims (21)

(57) [Claims]
1. A plurality of fine particles of an electron emitter terminated by a low work function material are partially arranged on a carbon body formed by using fine metal particles as a nucleus on a first substrate through oxygen. An electron-emitting device having a first electrode and a second electrode for applying a voltage for drawing electrons into a vacuum.
2. A second electrode, which applies a voltage for drawing the electrons into a vacuum, is arranged on the second substrate so as to face the first electrode on the first substrate. The electron-emitting device according to claim 1, wherein
3. A second electrode for applying a voltage for drawing the electrons into a vacuum is provided on a support body which is electrically insulated from the first electrode on the first substrate, The electron-emitting device according to claim 1, further comprising a third electrode that accelerates electrons.
4. The electron emitting device according to claim 1, wherein the metal of the metal fine particles is a catalytic metal.
5. The catalytic metal is Ni, Co, F
The electron-emitting device according to claim 4, wherein the electron group is an iron group of e or a platinum group of Pd or Ir, Pt.
6. The electron-emitting device according to claim 1, wherein the carbon body is graphite.
7. The electron-emitting device according to claim 1, wherein the low work function material is an alkali metal or an alkaline earth metal.
8. The electron-emitting device according to claim 7, wherein the alkali metal or alkaline earth metal is Cs, Ba, Ca or Sr.
9. The electron-emitting device according to claim 1, wherein the particle diameter of the fine particles of the electron emitter and the particle diameter of the metal fine particles are 3 to 100 nm. .
10. A method of manufacturing an electron-emitting device, comprising the steps of: (1) applying an organic metal-containing liquid onto an electrode arranged on a substrate, and then thermally decomposing it in a desired atmosphere to obtain fine metal particles or Forming fine particles composed of carbon fine particles and metal fine particles; (2) introducing a material having carbon into the base and decomposing it to generate a carbon body; and (3) having oxygen in the base. Heating or generating plasma in an atmosphere to terminate oxygen on the surface of the carbon body; and (4) introducing a low work function material into the substrate and coating fine particles of metal / carbon. (5) A method for manufacturing an electron-emitting device, comprising: manufacturing the substrate with a step of:
11. The method of manufacturing an electron-emitting device according to claim 10, wherein in the step (1), the organic metal-containing liquid is applied as droplets to the substrate by an inkjet method.
12. The method for manufacturing an electron-emitting device according to claim 11, wherein the inkjet method is a piezo jet method or a bubble jet method.
13. In the step (2), the material having carbon is C such as methane, ethane or propane.
A saturated hydrocarbon represented by n H 2n + 2 , an unsaturated hydrocarbon represented by a composition formula such as C n H 2n such as ethylene or propylene, or a cyclic hydrocarbon such as benzene. Item 13. A method for manufacturing an electron-emitting device according to any one of items 10 to 12.
14. The atmosphere having oxygen in the step (3) is an atmosphere of oxygen, oxygen and an inert gas (helium or the like), and / or N 2. 14. The method for manufacturing an electron-emitting device according to any one of items 1 to 13.
15. In the step (5), the heating temperature leaves only the low work function material having a structure in which oxygen terminated in the carbon and the low work function material are bonded together,
15. The temperature is not lower than the temperature at which the unbonded low work function material is removed by evaporation, or more.
Item 6. A method for manufacturing an electron-emitting device according to item.
16. The wiring comprises m first wirings provided on the first substrate and n second wirings to which a voltage for drawing the electrons into a vacuum is applied. The first wiring and the second wiring are substantially orthogonal to each other, and the electron emitting device according to any one of claims 1 to 9 is provided at an intersection of the first wiring and the second wiring. .
17. The n second wirings to which a voltage for drawing out the electrons to a vacuum is applied are arranged on the second substrate facing the first substrate, and a phosphor is provided. The image display device according to claim 16, comprising:
18. The n second electrodes, to which a voltage for drawing out into the vacuum is applied, are arranged on an electrically insulated support on the m first electrodes. ,And,
The image display device according to claim 16, further comprising a third electrode having a phosphor to which a voltage for accelerating the electrons is applied.
19. A method of manufacturing a display device, comprising: (1) forming a first wiring on a first substrate and then forming the first wiring;
Applying an organic metal-containing liquid onto the wiring of (1) and then thermally decomposing it to form fine metal particles or fine particles composed of fine carbon particles and fine metal particles, (2) a second base on the second base. Forming wiring and phosphor, (3) forming a vacuum container by supporting the first base and the second base with a support frame, (4) adding carbon to the first base Introducing a material having the same to decompose it to form a carbon body, (5) heating the inside of the vacuum vessel with an atmosphere containing oxygen, or generating plasma to terminate oxygen on the surface of the carbon body. (6) A step of introducing a low work function material into the vacuum container and coating with fine particles composed of metal / carbon, (7) A step of heating while exhausting the inside of the vacuum container, (8) The vacuum container To seal the A method of manufacturing a display device, comprising:
20. The method of manufacturing a display device according to claim 19, wherein the steps are performed in the order of (1) to (8).
21. A method of manufacturing a display device, comprising: (1) forming a first wiring on a first substrate, and then forming the first wiring.
After applying the organic metal-containing liquid on the wiring of 1, heating heat
Decomposes and decomposes metal particles or carbon particles and metal particles
And (2) introducing a material having carbon into the first substrate.
And decompose to form a carbon body, (3) The first substrate is placed in an atmosphere containing oxygen.
Of the carbon body by heating or generating plasma.
Terminating the surface with oxygen, (4) introducing a low work function material onto the first substrate
Then, the step of coating the fine particles of metal / carbon, (5) Forming the second wiring and the phosphor on the second substrate.
That step, (6) the first substrate and the second substrate, the support frame
A step of supporting and forming a vacuum container, (7) a step of heating while exhausting the inside of the vacuum container.
-Up method of manufacturing a display device characterized by comprising a step, sealing the vacuum vessel (8).
JP29710797A 1996-10-31 1997-10-29 Electron emitting device, image display device, and manufacturing method thereof Expired - Fee Related JP3372848B2 (en)

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JP29710797A JP3372848B2 (en) 1996-10-31 1997-10-29 Electron emitting device, image display device, and manufacturing method thereof
US08/961,277 US6008569A (en) 1996-10-31 1997-10-30 Electron emission device with electron-emitting fine particles comprised of a metal nucleus, a carbon coating, and a low-work-function utilizing this electron emission device
US09/468,940 US6129602A (en) 1996-10-31 1999-12-22 Methods of fabricating an electron emission device comprised of a metal nucleus, a carbon coating, and a low-work-function material and a method of fabricating an image display device utilizing this electron emission device

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